JP2002249676A - Near infrared ray reflective composite pigment - Google Patents
Near infrared ray reflective composite pigmentInfo
- Publication number
- JP2002249676A JP2002249676A JP2001331248A JP2001331248A JP2002249676A JP 2002249676 A JP2002249676 A JP 2002249676A JP 2001331248 A JP2001331248 A JP 2001331248A JP 2001331248 A JP2001331248 A JP 2001331248A JP 2002249676 A JP2002249676 A JP 2002249676A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- infrared
- infrared reflective
- group
- composite pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、近赤外線反射性お
よび／または近赤外線透過性色素で、白色顔料が被覆さ
れた近赤外線反射性複合顔料（以下単に「複合顔料」と
いう）、その製造方法並びに上記複合顔料により着色さ
れた塗料およびインキなどの近赤外線反射性被覆剤、お
よび該被覆剤で被覆された近赤外線反射材に関する。
尚、本発明において「近赤外線」とは、波長８００〜
２，０００ｎｍの光をいう。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a near-infrared reflective composite pigment (hereinafter simply referred to as "composite pigment") coated with a white pigment with a near-infrared reflective and / or near-infrared transparent dye, and a method for producing the same. Further, the present invention relates to a near-infrared reflective coating such as a paint and an ink colored with the composite pigment, and a near-infrared reflective material coated with the coating.
In the present invention, “near infrared” refers to a wavelength of 800 to
It refers to light of 2,000 nm.
【０００２】[0002]
【従来の技術】従来、建築物などの屋根や外壁などを塗
料で被覆した場合、屋根や外壁などの汚染などを目立た
なくする目的から暗色系塗料が使用されることが多い。
暗色系塗料に使用される顔料は、一般にカーボンブラッ
ク、アニリンブラック、酸化鉄ブラックなどであり、こ
れらの顔料は紫外線領域から遠赤外線領域までの波長の
光を吸収するものであることから、熱線、すなわち、近
赤外線を吸収し易く、直射日光により建築物などの室内
が高温になり易い。一方、建築物などの室内温度の上昇
を防止するための塗料として、酸化チタンなどの白色顔
料を含む太陽熱反射塗料が知られているが、この塗料は
熱遮蔽効果はあるものの、白色ないし淡色系塗料である
ため、汚染などが目立つことから、暗色系の太陽熱反射
塗料が求められている。2. Description of the Related Art Conventionally, when a roof or an outer wall of a building or the like is covered with a paint, a dark paint is often used for the purpose of making the roof or the outer wall or the like less noticeable.
Pigments used for dark paints are generally carbon black, aniline black, iron oxide black, and the like, and since these pigments absorb light having a wavelength from the ultraviolet region to the far infrared region, heat rays, That is, it is easy to absorb near-infrared rays and the interior of a building or the like tends to become hot due to direct sunlight. On the other hand, as a paint for preventing an increase in the indoor temperature of a building or the like, a solar heat reflective paint containing a white pigment such as titanium oxide is known, but this paint has a heat shielding effect, but is white or light color type. Since it is a paint, contamination and the like are conspicuous, so a dark-colored solar heat reflective paint is required.
【０００３】暗色系の太陽熱反射塗料については、特開
昭５６−１０９２５７号公報においては、三酸化アンチ
モン、ジクロム酸アンチモンなどの無機物を含む熱反射
塗料が提案されているが、上記無機物は重金属を含有す
る点で環境衛生上好ましくない。With respect to the dark-colored solar heat reflective paint, Japanese Patent Application Laid-Open No. 56-109257 proposes a heat reflective paint containing an inorganic substance such as antimony trioxide and antimony dichromate. It is not preferable in terms of environmental hygiene from the point of containing.
【０００４】上記とは異なり、建築物などの外壁の下地
に白色塗料を用いて塗装し、その上に赤外線反射性また
は赤外線透過性塗料を塗布し、直射日光の吸収を阻止
し、室内が高温になることを防止する塗料が提案されて
いる。この場合には、補修などの際に下地白コート（下
地としての白色塗料による塗装）の補修も必要となると
いう問題がある。[0004] Unlike the above, a white paint is applied to the base of an outer wall of a building or the like, and an infrared reflective or infrared transmissive paint is applied thereon to prevent the absorption of direct sunlight, and the indoor temperature is high. A paint that prevents the occurrence of a paint has been proposed. In this case, there is a problem that it is necessary to repair a base white coat (painting with a white paint as a base) at the time of repair or the like.
【０００５】一方、近年、レーザー、特に半導体レーザ
ーやそれに対するセンサーの発達により、従来一般に使
用されていたカーボンブラックやアニリンブラックなど
の黒色顔料にはない性質を有する黒色顔料を求める分野
が多くなっている。例えば、印刷インキ分野では、赤外
線反射性黒色顔料を含むインキで印刷し、肉眼で識別不
能な情報を赤外線リーダーなどで読み取ることができる
など、隠しバーコードの印刷や各種印刷物の偽造防止の
目的に使用される赤外線反射性黒色顔料を含むインキな
どが求められている。On the other hand, in recent years, with the development of lasers, especially semiconductor lasers and sensors therefor, there have been many fields seeking black pigments having properties not found in conventionally used black pigments such as carbon black and aniline black. I have. For example, in the printing ink field, printing with inks containing infrared reflective black pigments, information that cannot be identified with the naked eye can be read with an infrared reader, etc. There is a demand for an ink containing an infrared reflective black pigment to be used.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の事情を
鑑みてなされたものであり、本発明の目的は、塗料や印
刷インキなどの着色剤として使用され、特に塗料に使用
した場合には下地白コートが不要で、近赤外線を吸収せ
ずに、近赤外線を反射する有彩色または黒色の複合顔料
およびその製造方法を提供することである。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a colorant for use in paints and printing inks. It is an object of the present invention to provide a chromatic or black composite pigment which does not require a base white coat, reflects near infrared rays without absorbing near infrared rays, and a method for producing the same.
【０００７】本発明者らは、上記目的を達成すべく種々
検討した結果、近赤外線反射性および／または近赤外線
透過性の有彩色色素または黒色色素で、白色顔料を被覆
してなる複合顔料は、近赤外線を吸収せずに反射し、こ
れを着色剤とする塗料が塗布された建築物などは、直射
日光により室温が高温になりにくいことを見い出し、こ
の知見に基づいて本発明を完成した。The inventors of the present invention have conducted various studies to achieve the above object. As a result, a composite pigment obtained by coating a white pigment with a chromatic colorant or a black colorant having near-infrared reflectivity and / or near-infrared transmittance is obtained. Reflected without absorbing near-infrared rays, buildings and the like coated with a paint using this as a coloring agent, found that it is difficult for the room temperature to become high due to direct sunlight, and completed the present invention based on this finding. .
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明は、近
赤外線反射性および／または近赤外線透過性（以下「近
赤外線非吸収性」という）色素で、白色顔料を被覆して
なることを特徴とする近赤外線反射性複合顔料、その製
造方法、並びに着色剤として上記の複合顔料を含む近赤
外線反射性被覆剤、および基材が上記被覆剤で被覆され
た近赤外線反射材を提供する。That is, the present invention is characterized in that a white pigment is coated with a near-infrared reflecting and / or near-infrared transmitting (hereinafter referred to as "near-infrared non-absorbing") dye. The present invention provides a near-infrared reflective composite pigment, a method for producing the same, a near-infrared reflective coating containing the above-described composite pigment as a colorant, and a near-infrared reflective material in which a substrate is coated with the above-mentioned coating.
【０００９】[0009]
【発明の実施の形態】次に好ましい実施形態を挙げて本
発明をさらに詳細に説明する。本発明で使用する近赤外
線非吸収性色素としては、例えば、アゾ系、アンスラキ
ノン系、フタロシアニン系、ペリノン・ペリレン系、イ
ンジゴ・チオインジゴ系、ジオキサジン系、キナクリド
ン系、イソインドリノン系、イソインドリン系、ジケト
ピロロピロール系、アゾメチン系、アゾメチンアゾ系の
有機色素が挙げられ、好ましい黒色色素としてはアゾ
系、アゾメチンアゾ系、ペリレン系の有機黒色色素が挙
げられる。なお、「色素」とは「染料」または「顔料」
を意味するが、本発明においては顔料が好ましいので以
下「色素」を「顔料」という。Next, the present invention will be described in more detail with reference to preferred embodiments. As the near-infrared non-absorbing dye used in the present invention, for example, azo-based, anthraquinone-based, phthalocyanine-based, perinone-perylene-based, indigo-thioindigo-based, dioxazine-based, quinacridone-based, isoindolinone-based, isoindoline-based And diketopyrrolopyrrole-based, azomethine-based and azomethineazo-based organic dyes, and preferred black dyes include azo-based, azomethineazo-based and perylene-based organic dyes. "Dye" means "dye" or "pigment"
However, in the present invention, a pigment is preferable, and hence “dye” is hereinafter referred to as “pigment”.
【００１０】特に好ましい顔料は、下記一般式（Ｉ）で
表される近赤外線非吸収性黒色顔料である。 （但し、式中のＲは炭素数１〜３の低級アルキル基およ
び炭素数１〜３の低級アルコキシル基からなる群から選
ばれた基を表わし、ｎは１〜５の整数を表し、ｎが２以
上のときはＲは同じでも異なっていてもよい。）A particularly preferred pigment is a near-infrared non-absorbing black pigment represented by the following general formula (I). (Wherein, R in the formula represents a group selected from the group consisting of a lower alkyl group having 1 to 3 carbon atoms and a lower alkoxyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 5, and n represents When two or more, R may be the same or different.)
【００１１】上記黒色顔料は、下記の一般式（II）で表
わされる３−（アミノ−フェニルイミノ）−１−オキソ
−４，５，６，７−テトラクロルイソインドリンを従来
公知の方法でジアゾ化して得られるジアゾニウム塩をジ
アゾ成分とし、下記の一般式（III）で表わされる２−
ヒドロキシ−１１Ｈ−ベンゾ［ａ］−カルバゾール−３
−カルボキシアリールアミドをカップリング成分として
常法に従ってカップリングすることによって得ることが
できる。カップリング成分は１種または２種以上を混合
して使用することができる。また、ジアゾ成分およびカ
ップリング成分は、等当量で使用しても、また、いずれ
かが過剰または不足する量で使用しても構わない。The above-mentioned black pigment is prepared by converting 3- (amino-phenylimino) -1-oxo-4,5,6,7-tetrachloroisoindoline represented by the following general formula (II) into a diazo compound by a conventionally known method. A diazonium salt obtained by conversion into a diazo component is represented by the following general formula (III):
Hydroxy-11H-benzo [a] -carbazole-3
-Carboxyarylamide can be obtained by coupling according to a conventional method as a coupling component. One or more kinds of coupling components can be used in combination. Further, the diazo component and the coupling component may be used in an equivalent amount, or any of them may be used in excess or shortage.
【００１２】 （式中のＲおよびｎは前記定義の通りである。）[0012] (R and n in the formula are as defined above.)
【００１３】カップリング成分の具体例としては、例え
ば、２−ヒドロキシ−Ｎ−（２′−メチル−４′−メト
キシフェニル）−１１Ｈ−ベンゾ［ａ］−カルバゾール
−３−カルボキシアミド、２−ヒドロキシ−Ｎ−（４′
−メトキシフェニル）−１１Ｈ−ベンゾ［ａ］−カルバ
ゾール−３−カルボキシアミド、２−ヒドロキシ−Ｎ−
（２′−エチルフェニル）−１１Ｈ−ベンゾ［ａ］−カ
ルバゾール−３−カルボキシアミドなどが挙げられる。Specific examples of the coupling component include, for example, 2-hydroxy-N- (2'-methyl-4'-methoxyphenyl) -11H-benzo [a] -carbazole-3-carboxamide, 2-hydroxy -N- (4 '
-Methoxyphenyl) -11H-benzo [a] -carbazole-3-carboxamide, 2-hydroxy-N-
(2'-ethylphenyl) -11H-benzo [a] -carbazole-3-carboxamide and the like.
【００１４】上記のジアゾ成分のジアゾニウム塩とカッ
プリング成分とを常法に従い、水媒体あるいはｏ−ジク
ロルベンゼンなどの有機溶媒媒体中でカップリングさせ
ることにより、上記の一般式（Ｉ）で表わされる２−ヒ
ドロキシ−Ｎ−フェニル−１−｛［〔４−（４，５，
６，７−テトラクロロ−１−オキソ−２，３−ジヒドロ
−１Ｈ−イソインドール−３−イリデン）アミノ〕フェ
ニル］アゾ｝−１１Ｈ−ベンゾ［ａ］−カルバゾール−
３−カルボキシアミドである黒色アゾ顔料が得られる。
この黒色アゾ顔料は、優れた近赤外線非吸収性を有する
とともに、それよりも劣るものの、近赤外線反射性も有
している。By coupling the diazonium salt of the diazo component and the coupling component in an aqueous medium or an organic solvent medium such as o-dichlorobenzene according to a conventional method, the compound represented by the general formula (I) is obtained. 2-hydroxy-N-phenyl-1-{[[4- (4,5,
6,7-tetrachloro-1-oxo-2,3-dihydro-1H-isoindole-3-ylidene) amino] phenyl] azo} -11H-benzo [a] -carbazole-
A black azo pigment which is 3-carboxamide is obtained.
This black azo pigment has excellent near-infrared non-absorptivity and, although inferior thereto, also has near-infrared reflectivity.
【００１５】本発明で使用する白色顔料は、白色の無機
または有機の粉体であり、例えば、酸化チタン、亜鉛華
などの白色顔料、炭酸カルシウム、硫酸バリウム、アル
ミナ、シリカ、クレイ、活性白土、含水珪酸、無水珪
酸、アルミニウム粉末、ステンレス粉末、有機プラスチ
ックピグメントなどの体質顔料も白色顔料として挙げら
れる。これらの白色顔料は、１種または２種以上を組み
合わせて使用することができる。また、これらの白色顔
料は、いずれも市場から入手して本発明で使用すること
ができる。The white pigment used in the present invention is a white inorganic or organic powder, for example, white pigments such as titanium oxide and zinc white, calcium carbonate, barium sulfate, alumina, silica, clay, activated clay, and the like. Extender pigments such as hydrous silicic acid, anhydrous silicic acid, aluminum powder, stainless steel powder, and organic plastic pigments are also examples of white pigments. These white pigments can be used alone or in combination of two or more. In addition, all of these white pigments can be obtained from the market and used in the present invention.
【００１６】本発明の複合顔料は、近赤外線非吸収性顔
料の分散液と、白色顔料の粉末または分散液とを混合
し、乾燥することによって製造することができる。近赤
外線非吸収性顔料は、好ましくは分散剤を用いて液媒体
中に分散させた顔料分散液として使用する。The composite pigment of the present invention can be produced by mixing a dispersion of a near-infrared non-absorbing pigment with a powder or dispersion of a white pigment and drying. The near-infrared non-absorbing pigment is preferably used as a pigment dispersion liquid dispersed in a liquid medium using a dispersant.
【００１７】上記顔料を水性顔料分散液とする場合に、
本発明で使用する好ましい分散剤は、カルボキシル基や
スルホン酸基などのアニオン性基、アミノ基や第４級ア
ンモニウム基などのカチオン性基、水酸基やエーテル基
などのノニオン性基または上記イオン性基の何れかとノ
ニオン性基とを有する親水性高分子分散剤であり、従来
公知のいかなる高分子分散剤も使用可能である。When the pigment is used as an aqueous pigment dispersion,
The preferred dispersant used in the present invention is an anionic group such as a carboxyl group or a sulfonic acid group, a cationic group such as an amino group or a quaternary ammonium group, a nonionic group such as a hydroxyl group or an ether group, or the above ionic group. And a hydrophilic polymer dispersant having a nonionic group, and any conventionally known polymer dispersants can be used.
【００１８】例えば、アクリル酸、メタクリル酸、ジメ
チルアミノエチルメタクリレート、ヒドロキシエチルメ
タクリレートなどの親水性モノマーの少なくとも１種を
必須モノマーとし、これにスチレンや（メタ）アクリル
酸エステルなどを共重合させた親水性高分子、または多
価カルボン酸を多価アルコールに対して過剰で反応させ
て得られるポリエステル樹脂などが好ましく使用され
る。For example, at least one of hydrophilic monomers such as acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, and hydroxyethyl methacrylate is used as an essential monomer, and a hydrophilic polymer obtained by copolymerizing styrene, (meth) acrylic acid ester, etc. Polyester resins obtained by reacting a reactive polymer or a polycarboxylic acid with a polyhydric alcohol in excess are preferably used.
【００１９】高分子分散剤中の親水性モノマーの含有量
は、５〜８０質量％が好ましく、さらに好ましくは１０
〜４０質量％である。８０質量％を越えると分散剤の顔
料に対する吸着性が不充分となり、顔料の凝集や沈降が
生じ、一方、５質量％未満では分散剤の親水性が低下
し、顔料粒子自体は凝集や沈降しないが分散剤に包含さ
れたまま凝集および沈降する傾向が認められる。The content of the hydrophilic monomer in the polymer dispersant is preferably 5 to 80% by mass, more preferably 10 to 80% by mass.
４０40% by mass. If the amount exceeds 80% by mass, the adsorbability of the dispersant to the pigment becomes insufficient, causing aggregation or sedimentation of the pigment. If the amount is less than 5% by mass, the hydrophilicity of the dispersant decreases, and the pigment particles themselves do not aggregate or sediment. Tend to agglomerate and settle while being contained in the dispersant.
【００２０】本発明においては、上記高分子分散剤の分
子量が変化しても実質的に満足できる顔料分散液が得ら
れるが、分子量があまりに低過ぎると分散剤としての効
果が低下し、分子量が高過ぎると分散液の粘度が高くな
り過ぎ、高濃度の顔料分散液が得難くなる傾向を示す。
高分子分散剤の好ましい数平均分子量（ＧＰＣで測定、
標準ポリスチレンの分子量に換算）は３，０００〜１０
０，０００である。In the present invention, a substantially satisfactory pigment dispersion can be obtained even if the molecular weight of the polymer dispersant changes, but if the molecular weight is too low, the effect as a dispersant is reduced, and the molecular weight is lowered. If it is too high, the viscosity of the dispersion becomes too high, and it tends to be difficult to obtain a pigment dispersion having a high concentration.
Preferred number average molecular weight of the polymer dispersant (measured by GPC,
(Converted to the molecular weight of standard polystyrene) is 3,000 to 10
It is 0000.
【００２１】上記分散剤は、使用に際しては通常水溶性
の塩として用いられる。分散剤がアニオン性基を有する
場合には、塩を形成する塩基としては、例えば、ナトリ
ウム、カリウム、アンモニアが代表的であり、アミンと
してはモノ−、ジ−またはトリ−メチルアミン、モノ
−、ジ−またはトリ−エチルアミンなどの脂肪族第１乃
至第３級アミン；モノ−、ジ−またはトリ−エタノール
アミン、モノ−、ジ−またはトリ−プロパノールアミ
ン、メチルエタノールアミン、ジメチルエタノールアミ
ンなどのアルコールアミン；モルホリンおよびＮ−メチ
ルモルホリンなどのモルホリン類などが挙げられる。ま
た、上記分散剤がカチオン性基を有する場合には、例え
ば、塩を形成する酸としては酢酸、塩酸などが代表的な
酸として挙げられる。The dispersant is usually used as a water-soluble salt when used. When the dispersant has an anionic group, examples of the salt-forming base include, for example, sodium, potassium and ammonia, and the amine is mono-, di- or tri-methylamine, mono-, Aliphatic primary to tertiary amines such as di- or tri-ethylamine; alcohols such as mono-, di- or tri-ethanolamine, mono-, di- or tri-propanolamine, methylethanolamine, dimethylethanolamine Amines; and morpholines such as morpholine and N-methylmorpholine. When the dispersant has a cationic group, acetic acid, hydrochloric acid, and the like are typical examples of the acid that forms a salt.
【００２２】本発明においては、近赤外線非吸収性顔料
の分散液を調製する際、必要に応じて当該技術分野で使
用される各種の有彩色顔料や添加剤を本発明の効果が阻
害されない範囲で適宜使用できる。In the present invention, when preparing a dispersion of a near-infrared non-absorbing pigment, various chromatic pigments and additives used in the technical field may be used, if necessary, in a range where the effect of the present invention is not impaired. Can be used as appropriate.
【００２３】有彩色顔料としては、従来公知の有機およ
び無機顔料が使用でき、例えば、アゾ系、アンスラキノ
ン系、フタロシアニン系、ペリノン・ペリレン系、イン
ジゴ・チオインジゴ系、ジオキサジン系、キナクリドン
系、イソインドレノン系、イソインドリン系、ジケトピ
ロロピロール系、アゾメチン系、アゾメチンアゾ系、酸
化鉄系および複合酸化物系顔料などが挙げられる。As the chromatic color pigments, conventionally known organic and inorganic pigments can be used, for example, azo type, anthraquinone type, phthalocyanine type, perinone / perylene type, indigo / thioindigo type, dioxazine type, quinacridone type and isoindone type. Lenone, isoindoline, diketopyrrolopyrrole, azomethine, azomethineazo, iron oxide and composite oxide pigments.
【００２４】添加剤としては、例えば、紫外線吸収剤、
光安定剤、酸化防止剤、可塑剤、防錆剤、界面活性剤、
金属せっけん、滑剤、難燃剤などが挙げられる。As the additives, for example, ultraviolet absorbers,
Light stabilizer, antioxidant, plasticizer, rust inhibitor, surfactant,
Examples include metal soaps, lubricants, and flame retardants.
【００２５】本発明において顔料分散液の製造に使用す
る液媒体としては、水、水と親水性有機溶剤との混合物
および有機溶剤が用いられる。有機溶剤としては、例え
ば、エタノール、プロパノール、イソプロパノール、エ
チレングリコール、ジエチレングリコール、トリエチレ
ングリコール、プロピレングリコール、ジプロピレング
リコール、グリセリン、メチルセロソルブアセテート、
メチルカルビトール、エチルカルビトール、ブチルカル
ビトール、プロピレングリコールモノメチルエーテル、
プロピレングリコールモノメチルエーテルアセテートな
どのアルコールおよびそれらの誘導体などの親水性溶
剤、トルエン、キシレン、メチルエチルケトン、メチル
イソブチルケトン、シクロヘキサノンなどの塗料用やイ
ンキ用の溶剤およびそれらの混合物が挙げられる。In the present invention, water, a mixture of water and a hydrophilic organic solvent, and an organic solvent are used as a liquid medium for producing the pigment dispersion. Examples of the organic solvent include ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, methyl cellosolve acetate,
Methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether,
Examples include hydrophilic solvents such as alcohols and derivatives thereof such as propylene glycol monomethyl ether acetate, and solvents for paints and inks such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and mixtures thereof.
【００２６】本発明で使用する近赤外線非吸収性顔料の
分散液は、上記の構成成分を用いて製造される。製造方
法は従来公知の方法が採用でき、特に限定されない。例
えば、上記の各成分を配合し、これを、横型媒体分散
機、縦型媒体分散機、ボールミル、ホモミキサー、サン
ドグラインダー、スピードラインミル、ロールミルなど
の従来公知の分散機により顔料を液媒体中で混合摩砕す
る方式が代表的である。The dispersion of the near-infrared non-absorbing pigment used in the present invention is produced using the above-mentioned components. The production method can be a conventionally known method, and is not particularly limited. For example, the above components are blended, and the pigment is dispersed in a liquid medium by a conventionally known dispersing machine such as a horizontal media dispersing machine, a vertical media dispersing machine, a ball mill, a homomixer, a sand grinder, a speed line mill, and a roll mill. The method of mixing and grinding is typical.
【００２７】以上の如くして得られる顔料分散液におい
て、分散液中の近赤外線非吸収性顔料の含有量は、１０
〜５０質量％の範囲が好ましく、顔料の量が低過ぎる
と、前記白色顔料と混合した時に、近赤外線非吸収性顔
料の割合が少なくなり（液媒体の量が多くなり）、上記
顔料による白色顔料の被覆が不充分となる。一方、上記
顔料が多過ぎると顔料分散液による白色顔料の濡れ性が
不足するので好ましくない。また、使用する分散剤は顔
料１００質量部当たり約１０〜１００質量部が好ましい
範囲である。In the pigment dispersion obtained as described above, the content of the near-infrared non-absorbing pigment in the dispersion is 10%.
When the amount of the pigment is too low, the ratio of the near-infrared non-absorbing pigment decreases when the pigment is mixed with the white pigment (the amount of the liquid medium increases). Insufficient pigment coating. On the other hand, if the amount of the pigment is too large, the wettability of the white pigment with the pigment dispersion is insufficient, which is not preferable. The preferred range of the dispersant used is about 10 to 100 parts by mass per 100 parts by mass of the pigment.
【００２８】本発明の複合顔料は、白色顔料の粉末また
は分散液と近赤外線非吸収性顔料の分散液とを混合し、
乾燥することで得られる。白色顔料を粉末として使用す
る場合は、近赤外線非吸収性顔料の分散液を、両者の混
合物中の媒体の量が、混合物全体の５質量％以上から近
赤外線非吸収性顔料と白色顔料との混合物の吸油量また
は吸水量以下の範囲になる割合で混合することが好まし
い。両者の混合は、例えば、ヘンシェルミキサーの如き
高速粉体混合機を用いて数秒間〜数十分間行えばよい。
顔料分散液の使用量は、その顔料濃度によって異なる
が、固形分基準で白色顔料１００質量部に対して近赤外
線非吸収性顔料が５〜５００質量部になる範囲が好まし
い。The composite pigment of the present invention is obtained by mixing a powder or dispersion of a white pigment and a dispersion of a non-infrared non-absorbing pigment,
It is obtained by drying. When the white pigment is used as a powder, the dispersion of the near-infrared non-absorbing pigment is mixed with the dispersion of the near-infrared non-absorbing pigment and the white pigment in an amount of 5% by mass or more of the mixture. It is preferable to mix the mixture at a ratio within the range of the oil absorption or water absorption of the mixture. The mixing of the two may be performed for several seconds to several tens of minutes using a high-speed powder mixer such as a Henschel mixer.
The amount of the pigment dispersion varies depending on the pigment concentration, but is preferably in the range of 5 to 500 parts by mass of the non-infrared non-absorbing pigment based on 100 parts by mass of the white pigment on a solid content basis.
【００２９】白色顔料を分散液として使用する場合に
は、近赤外線非吸収性顔料の場合と同様に、高分子分散
剤を用いて液媒体中に分散させた白色顔料分散液を使用
することが好ましい。分散媒体としては前記の近赤外線
非吸収性顔料の場合と同じ溶剤が使用できる。分散液中
の白色顔料の含有量は、特に限定されないが、２０〜５
０質量％程度が好ましい。高分子分散剤の使用量は近赤
外線非吸収性顔料の場合と同じである。When a white pigment is used as a dispersion, a white pigment dispersion dispersed in a liquid medium using a polymer dispersant may be used as in the case of a near-infrared non-absorbing pigment. preferable. As the dispersing medium, the same solvent as in the case of the near-infrared non-absorbing pigment can be used. The content of the white pigment in the dispersion is not particularly limited, but is preferably 20 to 5%.
About 0% by mass is preferable. The amount of the polymer dispersant used is the same as in the case of the near infrared non-absorbing pigment.
【００３０】白色顔料分散液を、近赤外線非吸収性顔料
の分散液と混合する場合は、例えば、ディゾルバーなど
の従来から用いられる混合機が使用でき、分散剤として
イオン性高分子分散剤を用いた場合には、分散液のｐＨ
を変えるか、あるいは分散剤を多価金属イオンで水不溶
性塩にして白色顔料を近赤外線非吸収性顔料により被覆
する。特にアニオン性高分子分散剤を用いた場合には、
アルミニウム、アルカリ土類金属などの塩の水溶液を少
量添加することによって、分散剤中に存在しているアニ
オン性基をこれらのカチオンによって造塩させ、水不溶
性にして、白色顔料と近赤外線非吸収性顔料との結合力
を高めることができる。また、白色顔料が、例えば、ア
ルカリ土類金属などの多価金属塩である場合には、上記
の如く特別に多価金属イオンを添加しなくても、多価金
属塩である白色顔料の表面において分散剤が水不溶化さ
れ、同様の作用効果を奏する。When a white pigment dispersion is mixed with a dispersion of a near-infrared non-absorbing pigment, a conventional mixer such as a dissolver can be used, and an ionic polymer dispersant is used as a dispersant. If present, the pH of the dispersion
Alternatively, the white pigment is coated with a near-infrared non-absorbing pigment by changing the dispersant to a water-insoluble salt with a polyvalent metal ion. Especially when using an anionic polymer dispersant,
By adding a small amount of an aqueous solution of a salt of aluminum, alkaline earth metal, etc., the anionic groups present in the dispersant are salt-formed by these cations, made water-insoluble, and non-absorbing white pigments and near infrared rays. The bonding force with the functional pigment can be increased. When the white pigment is, for example, a polyvalent metal salt such as an alkaline earth metal, the surface of the white pigment, which is a polyvalent metal salt, can be prepared without adding a polyvalent metal ion as described above. In the above, the dispersant is insolubilized with water, and the same action and effect can be obtained.
【００３１】本発明の複合顔料は、白色顔料の粉末また
は分散液と近赤外線非吸収性顔料の分散液との混合物を
任意の乾燥方法によって乾燥することで得られるが、粉
末状の上記組成物が得られるスプレー式乾燥方法が特に
適している。The composite pigment of the present invention can be obtained by drying a mixture of a powder or a dispersion of a white pigment and a dispersion of a non-infrared non-absorbing pigment by any drying method. Is particularly suitable.
【００３２】本発明の複合顔料は、塗料用ビヒクルまた
はインキ用ビヒクルと混合して、近赤外線反射塗料およ
びインキとすることができる。ビヒクルは、塗料やイン
キの製造に通常使用される合成または天然の樹脂、油、
溶剤などであり、これらのビヒクルは塗料やインキで従
来から使用されているものがいずれも使用可能であり、
特に限定されるものではない。The composite pigment of the present invention can be mixed with a vehicle for paints or a vehicle for inks to obtain near infrared reflective paints and inks. Vehicles are made of synthetic or natural resins, oils,
Solvents, etc., and these vehicles can be used any of those conventionally used in paints and inks,
There is no particular limitation.
【００３３】例えば、塗料用のビヒクル樹脂としては、
例えば、乾性油、ロジンやギルソナイトなどの天然樹
脂、アルキッド樹脂、アミノ樹脂、エポキシ樹脂、不飽
和ポリエステル樹脂、ビニル樹脂、アクリル樹脂、ポリ
ウレタン樹脂などが、インキ用のビヒクル樹脂として
は、例えば、上記の天然樹脂、石油樹脂、フェノール樹
脂、アルキッド樹脂、ビニル樹脂、ポリアミド樹脂、ア
クリル樹脂、ニトロセルロースなどが挙げられる。これ
らのビヒクル樹脂と複合顔料との使用割合も、従来の塗
料における顔料とビヒクル樹脂との使用割合と同様であ
り、特に限定されない。For example, as a vehicle resin for paint,
For example, drying oils, natural resins such as rosin and Gilsonite, alkyd resins, amino resins, epoxy resins, unsaturated polyester resins, vinyl resins, acrylic resins, polyurethane resins, and the like, as vehicle resins for ink, for example, Examples include natural resins, petroleum resins, phenol resins, alkyd resins, vinyl resins, polyamide resins, acrylic resins, nitrocellulose, and the like. The usage ratio between the vehicle resin and the composite pigment is also the same as the usage ratio between the pigment and the vehicle resin in the conventional paint, and is not particularly limited.
【００３４】本発明の近赤外線反射性塗料およびインキ
などの被覆剤は、従来公知の分散機、例えば、横型媒体
分散機、縦型媒体分散機、ボールミル、ローラーミル、
ディスパーなどにより、複合顔料と上記ビヒクルとから
得ることができる。The coating agent such as the near-infrared reflective paint and ink of the present invention can be prepared by using a conventionally known dispersing machine such as a horizontal media dispersing machine, a vertical media dispersing machine, a ball mill, a roller mill, and the like.
It can be obtained from the composite pigment and the above vehicle by a disper or the like.
【００３５】上記で得られる近赤外線反射性塗料を用い
る塗装方法には、例えば、刷毛、ローラー、エアースプ
レーガンなどの従来公知の塗装方法を適用でき、被覆さ
れる基材は、特に限定されるものではなく、例えば、ア
ルミ板、鉄板などの金属基材、アクリル樹脂、ポリカー
ボネートなどのプラスチック、木材、ガラスやセラミッ
クスなどの無機材料などが挙げられる。As a coating method using the near-infrared reflective paint obtained above, for example, a conventionally known coating method such as a brush, a roller, an air spray gun or the like can be applied, and the substrate to be coated is particularly limited. For example, a metal base such as an aluminum plate or an iron plate, a plastic such as an acrylic resin or a polycarbonate, a wood, an inorganic material such as a glass or a ceramic, or the like can be used.
【００３６】上記で得られる近赤外線反射インキを用い
る印刷方法としては、例えば、凸版印刷、平版印刷、凹
版印刷、グラビア印刷、スクリーン印刷、電子写真プリ
ント、インクジェットプリント、熱転写プリントなどが
挙げられ、塗布方法としては、例えば、ブレードコータ
ー、ロッドコーター、ナイフコーター、スクイズコータ
ー、エアドクターコーター、グラビアコーター、スプレ
ーコーター、レーザープリンター、インクジェットプリ
ンター、熱転写プリンターなどが挙げられる。Examples of the printing method using the near-infrared reflective ink obtained above include letterpress printing, planographic printing, intaglio printing, gravure printing, screen printing, electrophotographic printing, ink jet printing, and thermal transfer printing. Examples of the method include a blade coater, a rod coater, a knife coater, a squeeze coater, an air doctor coater, a gravure coater, a spray coater, a laser printer, an ink jet printer, and a thermal transfer printer.
【００３７】上記のインキで被覆される基材は、特に限
定されるものではなく、例えば、紙、化学繊維混抄紙、
合成紙、不織布、織布、プラスチックフィルム、プラス
チックシート、プラスチック、金属、木材、ガラス、セ
ラミックスなどの従来公知の印刷あるいは塗布可能な基
材が使用される。The substrate to be coated with the above-mentioned ink is not particularly limited, and examples thereof include paper, synthetic fiber mixed paper,
Conventionally known printable or coatable substrates such as synthetic paper, nonwoven fabric, woven fabric, plastic film, plastic sheet, plastic, metal, wood, glass, and ceramics are used.
【００３８】[0038]
【実施例】次に実施例および比較例を挙げて本発明をさ
らに具体的に説明する。尚、文中、「部」または「％」
とあるのは特に断りのない限り質量基準である。Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, "part" or "%"
“A” is based on mass unless otherwise specified.
【００３９】実施例１ 前記一般式（Ｉ）で表わされる黒色顔料（２−ヒドロキ
シ−Ｎ−（２’−メチル−４’−メトキシフェニル）−
１−｛［４−［（４，５，６，７−テトラクロロ−１−
オキソ−２，３−ジヒドロ−１Ｈ−イソインドール−３
−イリデン）アミノ］フェニル］アゾ｝−１１Ｈ−ベン
ゾ［ａ］−カルバゾール−３−カルボキシアミド）２０
０部、スチレン−アクリル酸共重合体のアンモニウム塩
水溶液（固形分４０％）２００部および水４００部を横
型媒体分散機で分散処理して黒色顔料の分散液を得た。Example 1 A black pigment represented by the general formula (I) (2-hydroxy-N- (2'-methyl-4'-methoxyphenyl)-
1-{[4-[(4,5,6,7-tetrachloro-1-
Oxo-2,3-dihydro-1H-isoindole-3
-Ylidene) amino] phenyl] azo} -11H-benzo [a] -carbazole-3-carboxamide) 20
0 parts, 200 parts of an aqueous solution of ammonium salt of styrene-acrylic acid copolymer (solid content: 40%) and 400 parts of water were subjected to dispersion treatment with a horizontal medium disperser to obtain a black pigment dispersion.
【００４０】一方、水５００部に酸化チタン顔料２００
部をホモミキサーで十分解膠する。この酸化チタン分散
液に上記分散液６００部を注入し、さらに１時間攪拌す
る。その後、希酢酸水溶液を滴下し、ｐＨを約４〜５と
し、黒色顔料で酸化チタン顔料を被覆する。その後、ろ
過、水洗し、熱風乾燥および粉砕し、本発明の複合顔料
を得た。On the other hand, titanium oxide pigment 200 was added to 500 parts of water.
The part is peptized sufficiently with a homomixer. 600 parts of the above dispersion liquid is poured into this titanium oxide dispersion liquid, and further stirred for 1 hour. Thereafter, a diluted acetic acid aqueous solution is dropped to adjust the pH to about 4 to 5, and the titanium oxide pigment is coated with a black pigment. Thereafter, the mixture was filtered, washed with water, dried with hot air and pulverized to obtain the composite pigment of the present invention.
【００４１】実施例２ ヘンシェルミキサーに酸化チタン顔料５００部を入れ、
高速撹拌しながら、実施例１の黒色顔料分散液を１５分
間で６００部をスプレーで加えた後、熱風で乾燥し、本
発明の複合顔料を得た。Example 2 500 parts of a titanium oxide pigment was placed in a Henschel mixer.
While stirring at high speed, 600 parts of the black pigment dispersion of Example 1 was added by spraying over 15 minutes, and then dried with hot air to obtain a composite pigment of the present invention.
【００４２】実施例３ 実施例１の黒色顔料に代えて、Ｃ．Ｉ．ピグメントブル
ー１５（青色顔料）５５部、Ｃ．Ｉ．ピグメントレッド
５７（赤色顔料）１００部およびＣ．Ｉ．ピグメントエ
ロー１７（黄色顔料）４５部を使用して、実施例１と同
様に黒色顔料分散液を調製し、実施例１と同様にして酸
化チタン分散液に添加し、本発明の複合顔料を得た。Example 3 In place of the black pigment of Example 1, C.I. I. Pigment Blue 15 (blue pigment), 55 parts of C.I. I. Pigment Red 57 (red pigment) and 100 parts of C.I. I. Using 45 parts of CI Pigment Yellow 17 (yellow pigment), a black pigment dispersion was prepared in the same manner as in Example 1, and added to the titanium oxide dispersion in the same manner as in Example 1 to obtain the composite pigment of the present invention. Was.
【００４３】実施例４ 実施例１の黒色顔料に代えて、Ｃ．Ｉ．ピグメントブラ
ック３２（黒色顔料）２００部を使用して、実施例１と
同様に黒色顔料分散液を調製し、実施例１と同様にして
酸化チタン分散液に添加し、本発明の複合顔料を得た。Example 4 In place of the black pigment of Example 1, C.I. I. Using 200 parts of CI Pigment Black 32 (black pigment), a black pigment dispersion was prepared in the same manner as in Example 1, and added to the titanium oxide dispersion in the same manner as in Example 1 to obtain the composite pigment of the present invention. Was.
【００４４】実施例５〜８ 実施例１または２と同様な方法で下記表１の複合顔料を
得た。 Examples 5 to 8 In the same manner as in Example 1 or 2, composite pigments shown in Table 1 below were obtained.
【００４５】実施例９〜１２ 下記表２のＣ．Ｉ．ジアゾコンポーネントをジアゾ化
し、下記表２のＣ．Ｉ．カップリングコンポーネントと
カップリング反応を行って夫々の黒色顔料を得た。これ
らの黒色顔料を用い、実施例１または実施例２と同様な
方法で複合顔料を得た。 Examples 9 to 12 I. The diazo component was diazotized, and C.I. I. A coupling reaction was performed with the coupling component to obtain each black pigment. Using these black pigments, a composite pigment was obtained in the same manner as in Example 1 or Example 2.
【００４６】実施例１３ 実施例１の複合顔料を用いて下記の処方で塗料の調製を
行った。実施例１の複合顔料３部、ベースワニス１２
部、シンナー６部およびガラスビーズ４８部を１００ｍ
ｌのガラス瓶に取り、ペイントシェイカーで９０分間振
とうした後、ベースワニス３９部を加えて、さらに１０
分間同機にて振とうし、熱硬化アルキッド塗料を調製し
た。Example 13 Using the composite pigment of Example 1, a paint was prepared according to the following formulation. 3 parts of composite pigment of Example 1, base varnish 12
Part, 6 parts of thinner and 48 parts of glass beads are 100 m
After shaking for 90 minutes with a paint shaker, add 39 parts of base varnish, and further add 10 parts.
The mixture was shaken for one minute with the same machine to prepare a thermosetting alkyd paint.
【００４７】上記処方において、ベースワニスは、スー
パーベッカミンＪ−８２０（大日本インキ社製）７０％
とフタルキッド１３３−６０（日立化成社製）３０％よ
りなるものであり、シンナーはキシレン８０％とブタノ
ール２０％よりなるものである。カーボンブラック塗料
を塗装をした鋼板に、この塗料をバーコーターＮｏ．４
０を用いて塗布し、１３５℃×３０分で硬化させた。In the above formulation, the base varnish was made of Super Beckamine J-820 (manufactured by Dainippon Ink) 70%
And phthalkid 133-60 (manufactured by Hitachi Chemical Co., Ltd.), and the thinner is composed of 80% xylene and 20% butanol. This paint was applied to a steel plate coated with a carbon black paint, using a bar coater No. 4
And then cured at 135 ° C. for 30 minutes.
【００４８】実施例１４〜１６ 実施例２〜４の複合顔料を用いて実施例１３と同一の処
方で塗料の調製を行った。カーボンブラック塗料を塗装
した鋼板に、この塗料をバーコーターＮｏ．４０を用い
て塗布し、１３５℃×３０分で硬化させた。Examples 14 to 16 Using the composite pigments of Examples 2 to 4, coating materials were prepared in the same manner as in Example 13. This paint was applied to a steel plate coated with carbon black paint using a bar coater No. The composition was applied using a coating No. 40 and cured at 135 ° C. for 30 minutes.
【００４９】比較例１ 実施例１と同じ黒色顔料を用い、実施例１３と同一の処
方で塗料を調製した。カーボンブラック塗料を塗装した
鋼板に、この塗料をバーコーターＮｏ．４０を用いて塗
布し、１３５℃×３０分で硬化させた。Comparative Example 1 A coating material was prepared using the same black pigment as in Example 1 and using the same formulation as in Example 13. This paint was applied to a steel plate coated with carbon black paint using a bar coater No. The composition was applied using a coating No. 40 and cured at 135 ° C. for 30 minutes.
【００５０】比較例２〜３ 実施例３〜４に使用したと同じ黒色顔料を、比較例１と
同様にベースワニスに分散して塗料を調製した。カーボ
ンブラック塗料を塗装した鋼板に、この塗料をバーコー
ターＮｏ．４０を用いて塗布し、１３５℃×３０分で硬
化させた。Comparative Examples 2-3 The same black pigment used in Examples 3 and 4 was dispersed in a base varnish in the same manner as in Comparative Example 1 to prepare a paint. This paint was applied to a steel plate coated with carbon black paint using a bar coater No. The composition was applied using a coating No. 40 and cured at 135 ° C. for 30 minutes.
【００５１】実施例１７（昇温テスト） 厚さ１５ｍｍの発泡スチロール製昇温テスト断熱槽上
に、実施例１３〜１６および比較例１〜３のテスト板１
５０×７０×１ｍｍを乗せ、該テスト板上の４００ｍｍ
上から光（２５０Ｗ赤外線ランプ）を照射し、１分、５
分、１０分および３０分毎にテスト板表面と槽内の温度
を測定した。Example 17 (Temperature Elevation Test) The test plates 1 of Examples 13 to 16 and Comparative Examples 1 to 3 were placed on a 15-mm-thick styrene foam temperature increase test insulated tank.
Place 50 × 70 × 1 mm, 400 mm on the test plate
Irradiate light (250W infrared lamp) from above, 1 minute, 5 minutes
Every 10 minutes and every 30 minutes, the temperature of the test plate surface and the temperature in the bath were measured.
【００５２】試験結果を表３に示す。複合化していない
顔料を用いた比較例１〜３は、下地のカーボンブラック
塗料の影響を受け、比較例１〜３の温度上昇は、表面温
度、槽内温度ともに複合顔料を用いた実施例１３〜１６
より大きい。３０分後の槽内の温度差は１０℃程度にな
っている。実施例１３〜１６の複合顔料を含む塗料で塗
装された近赤外線反射材は優れた近赤外線遮蔽性を有し
ている。Table 3 shows the test results. Comparative Examples 1 to 3 using uncomposited pigments were affected by the carbon black paint as the base, and the temperature rises of Comparative Examples 1 to 3 were caused by Example 13 in which both the surface temperature and the temperature in the tank used the composite pigment. ~ 16
Greater than. The temperature difference in the tank after 30 minutes is about 10 ° C. The near-infrared reflective materials coated with the paints containing the composite pigments of Examples 13 to 16 have excellent near-infrared shielding properties.
【００５３】 [0053]
【００５４】実施例１８ 実施例１の複合顔料３０部、オフセット平版インキ用調
合ワニス６１．７部、ドライヤー０．８部およびインキ
ソルベント７．５部にてオフセット平版印刷用黒色イン
キを調製し、白アート紙にオフセット印刷機にてスクリ
ーン線数を１５０線で平網濃度１００％にて全面印刷し
た。Example 18 A black ink for offset lithographic printing was prepared using 30 parts of the composite pigment of Example 1, 61.7 parts of a preparation varnish for offset lithographic ink, 0.8 parts of a drier and 7.5 parts of ink solvent. The entire surface was printed on white art paper with an offset printing machine at a screen ruling of 150 and a screen density of 100%.
【００５５】上記オフセット平版インキ用調合ワニス
は、ロジン変性フェノール樹脂、乾性油変性イソフタル
酸アルキッドおよび乾性油を主成分とし、インキソルベ
ントおよびアルミニウムキレートを加えたものである。The above-mentioned varnish for offset lithographic ink contains rosin-modified phenolic resin, dry oil-modified alkyd isophthalate and drying oil as main components, and ink ink and aluminum chelate are added.
【００５６】実施例１９ 実施例１８の黒色インキを用いて、実施例１８の白アー
ト紙の代わりに黒アート紙に全面印刷した。 実施例２０ 実施例９の複合顔料を用いて実施例１８と同様にオフセ
ット平版印刷用黒色インキを調製し、白アート紙にオフ
セット印刷した。 実施例２１ 実施例２０の黒色インキを用いて、実施例２０の白アー
ト紙の代わりに黒アート紙に全面印刷した。Example 19 Using the black ink of Example 18, the entire surface was printed on black art paper instead of the white art paper of Example 18. Example 20 Using the composite pigment of Example 9, a black ink for offset lithographic printing was prepared in the same manner as in Example 18, and offset printing was performed on white art paper. Example 21 Using the black ink of Example 20, the entire surface was printed on black art paper instead of the white art paper of Example 20.
【００５７】比較例４〜５ 実施例１と９で使用した複合化されていない黒色顔料２
３部、オフセット平版インキ用調合ワニス７１．２部、
ドライヤー０．８部およびインキソルベント５部にて２
種のオフセット平版印刷用黒色インキを調製し、実施例
１８と同様に白アート紙にそれぞれオフセット印刷し
た。 比較例６〜７ 比較例４〜５の２種の黒色インキを用いて、比較例４〜
５の白アート紙の代わりに黒アート紙にそれぞれ全面印
刷した。Comparative Examples 4-5 Uncomplexed black pigment 2 used in Examples 1 and 9
3 parts, preparation varnish for offset lithographic ink 71.2 parts,
2 with 0.8 parts of dryer and 5 parts of ink solvent
Various kinds of black inks for offset lithographic printing were prepared, and offset printing was performed on white art paper in the same manner as in Example 18. Comparative Examples 6 and 7 Comparative Examples 4 and 5 were performed using the two types of black inks of Comparative Examples 4 and 5.
5 was printed on black art paper instead of white art paper.
【００５８】実施例２２ 実施例１８〜２１および比較例４〜７の印刷物の可視光
線および赤外線に対する性質を見るために、印刷物の裏
からアルミナ白板を当てて日立製作所製３３０型自記分
光光度計を用いて紫外部−可視部−近赤外部の反射率を
測定し、その結果を表４に示した。Example 22 In order to observe the properties of the printed materials of Examples 18 to 21 and Comparative Examples 4 to 7 with respect to visible light and infrared light, an alumina white plate was applied from the back of the printed material to a 330-type self-recording spectrophotometer manufactured by Hitachi, Ltd. The UV-visible-near-infrared reflectance was measured using this method, and the results are shown in Table 4.
【００５９】 [0059]
【００６０】表４の結果より、本発明の複合顔料を用い
た実施例１８〜２１の印刷物は紫外部および可視部にお
いてほとんど反射を示さず、吸収しているため当然黒色
を示すが、近赤外部においては反射を示している。特に
白アート紙に印刷した実施例１８、２０および比較例４
〜５は基材の白の影響を受け反射率は高い。一方、黒ア
ート紙に印刷した実施例１９、２１は、複合顔料が中心
に酸化チタン顔料を核として有するため、近赤外部にお
いて約８０％の反射率を示す。From the results shown in Table 4, the printed materials of Examples 18 to 21 using the composite pigment of the present invention hardly show reflection in the ultraviolet and visible regions, and naturally exhibit black color because they absorb light. Reflection is shown outside. In particular, Examples 18 and 20 and Comparative Example 4 printed on white art paper
Nos. 5 to 5 are high in reflectivity due to the influence of white of the substrate. On the other hand, Examples 19 and 21 printed on black art paper show a reflectance of about 80% in the near infrared region because the composite pigment has a titanium oxide pigment at the center.
【００６１】しかし、複合化していない顔料を用いた比
較例６〜７の印刷物は、近赤外部の反射が基材の黒に吸
収され、反射率が約４０％以下と小さい。以上のことか
ら実施例１８〜２１および比較例４〜７の印刷物は、い
ずれも肉眼で見た際には黒色を示し、識別不能である
が、近赤外線の照射に対しては反射率に差異を示す。本
発明の近赤外線反射インキは、従来のカーボンブラック
などの黒色インキと白色および黒色などの基材色と組み
合わせ、近赤外線に対するこれらの性質の差異を赤外線
リーダーなどで読み取ることにより、隠しバーコードや
偽造防止を目的とする印刷用途に適用できる。However, in the printed materials of Comparative Examples 6 and 7 using non-composite pigments, the reflection in the near-infrared region was absorbed by the black base material, and the reflectance was as small as about 40% or less. From the above, the printed materials of Examples 18 to 21 and Comparative Examples 4 to 7 all show black when viewed with the naked eye and are indistinguishable, but have different reflectances to near-infrared radiation. Is shown. The near-infrared reflective ink of the present invention combines a conventional black ink such as carbon black with a base color such as white and black, and reads a difference in these properties with respect to near-infrared light with an infrared reader or the like, so that a hidden barcode or the like can be obtained. It can be applied to printing for the purpose of preventing forgery.
【００６２】[0062]
【発明の効果】以上の如き本発明によれば、下記の特徴
を有する複合顔料が提供される。 （１）本発明の複合顔料は、微分散された近赤外線非吸
収性顔料が、白色顔料の表面に吸着されているため、該
複合顔料を媒体中に分散させても白色顔料と近赤外線非
吸収性顔料との色分れが発生せず、しかも同量の近赤外
線非吸収性顔料に比較して著しく濃度が高く、且つ安価
である。According to the present invention as described above, a composite pigment having the following characteristics is provided. (1) In the composite pigment of the present invention, since the finely dispersed near-infrared non-absorbing pigment is adsorbed on the surface of the white pigment, even if the composite pigment is dispersed in a medium, the white pigment and the near-infrared non-absorbing pigment are dispersed. No color separation occurs with the absorbing pigment, and the density is remarkably higher than that of the near-infrared non-absorbing pigment of the same amount, and the cost is low.
【００６３】（２）本発明の複合顔料は、微分散された
近赤外線非吸収性顔料が白色顔料の表面に吸着されてい
るため、該複合顔料の外観は近赤外線非吸収性顔料と同
様な色であり、核として白色顔料を含有するため、近赤
外線非吸収性顔料自体の性能より近赤外線の吸収は低
く、塗料やインキに用いた場合、該塗料やインキにより
被覆されたものは、直射日光により高温になりにくく、
優れた近赤外線遮蔽効果を発揮できる。(2) Since the finely dispersed near-infrared non-absorbing pigment is adsorbed on the surface of the white pigment, the composite pigment of the present invention has the same appearance as the near-infrared non-absorbing pigment. Because it is a color and contains a white pigment as a nucleus, the absorption of near-infrared light is lower than the performance of the near-infrared non-absorbing pigment itself, and when used in paints and inks, those coated with the paints and inks are directly irradiated. It is hard to become high temperature by sunlight,
Excellent near-infrared shielding effect can be exhibited.
【００６４】（３）本発明の複合顔料を含む近赤外線反
射塗料を塗布した近赤外線反射材は、従来必要であった
下地白コートなどが不要であり、上記塗料自体の性能に
より近赤外線遮蔽効果を発揮できる。また、補修などの
際も下地白コートなどを塗布する必要がない。(3) The near-infrared reflective material coated with the near-infrared reflective paint containing the composite pigment of the present invention does not require a base white coat or the like which has been conventionally required. Can be demonstrated. In addition, it is not necessary to apply a base white coat or the like at the time of repair or the like.
【００６５】（４）本発明の複合顔料を含む近赤外線反
射インキで印刷または被覆した近赤外線反射材は、肉眼
で識別不能な情報を赤外線リーダーなどで読み取ること
ができるので、本発明のインキを用いて隠しバーコード
や偽造防止印刷部を有する印刷物を提供できる。(4) The near-infrared reflective material printed or coated with the near-infrared reflective ink containing the composite pigment of the present invention can read information that cannot be identified with the naked eye with an infrared reader or the like. A printed material having a hidden barcode or a forgery prevention printing portion can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡本 久男 東京都中央区日本橋馬喰町１−７−６ 大 日精化工業株式会社内 (72)発明者 細田 徹 東京都中央区日本橋馬喰町１−７−６ 大 日精化工業株式会社内 (72)発明者 阿部 好夫 東京都中央区日本橋馬喰町１−７−６ 大 日精化工業株式会社内 (72)発明者 中村 道衛 東京都中央区日本橋馬喰町１−７−６ 大 日精化工業株式会社内 Ｆターム(参考） 4J038 BA201 BA221 CF001 CG032 CG142 CH202 CJ032 CJ132 DA111 DB001 DD121 DD181 DG001 JA15 JA32 JA34 JB16 JB18 JB27 JB28 JB38 JC36 KA08 KA09 PC02 PC03 PC06 PC08 4J039 AB00 AB02 AB03 AB04 AD02 AD06 AD07 AD08 AD09 AD10 AE06 AE08 BC16 BC17 BC44 BC50 BC51 BC53 BC54 BC60 BC69 FA01 FA02 FA03 FA04 FA05 FA07 GA01 GA02 GA03 GA06 GA10 GA24 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hisao Okamoto 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Dai-Nissei Chemical Industry Co., Ltd. (72) Inventor Toru Hosoda 1-7-6 Nihonbashi Bakurocho, Chuo-ku, Tokyo Within Dai Nissin Chemical Industry Co., Ltd. (72) Yoshio Abe 1-7-6 Nihombashi Bakurocho, Chuo-ku, Tokyo Inside Nissei Chemical Industry Co., Ltd. (72) Michie Nakamura 1-7- Nihonbashi Bakurocho, Chuo-ku, Tokyo 6 Dai Nissei Chemical Co., Ltd. F-term (reference) 4J038 BA201 BA221 CF001 CG032 CG142 CH202 CJ032 CJ132 DA111 DB001 DD121 DD181 DG001 JA15 JA32 JA34 JB16 JB18 JB27 JB28 JB38 JC36 KA08 KA09 PC02 PC03 PC06 PC08 4J039 AB00 AD02 AB02 AD08 AD09 AD10 AE06 AE08 BC16 BC17 BC44 BC50 BC51 BC53 BC54 BC60 BC69 FA01 FA02 FA03 FA04 FA05 FA07 GA01 GA02 GA03 GA06 GA10 GA2 Four
Claims (10)
透過性色素で、白色顔料を被覆してなることを特徴とす
る近赤外線反射性複合顔料。1. A near-infrared reflective composite pigment obtained by coating a white pigment with a near-infrared reflective and / or near-infrared transmissive dye.
透過性色素が、アゾ系、アンスラキノン系、フタロシア
ニン系、ペリノン・ペリレン系、インジゴ・チオインジ
ゴ系、ジオキサジン系、キナクリドン系、イソインドリ
ノン系、イソインドリン系、ジケトピロロピロール系、
アゾメチン系およびアゾメチンアゾ系の有機色素からな
る群から選ばれた少なくとも一種である請求項１に記載
の近赤外線反射性複合顔料。2. The near-infrared reflective and / or near-infrared transmissive dye is an azo-based, anthraquinone-based, phthalocyanine-based, perinone-perylene-based, indigo-thioindigo-based, dioxazine-based, quinacridone-based, or isoindolinone-based dye. Isoindoline type, diketopyrrolopyrrole type,
The near-infrared reflective composite pigment according to claim 1, which is at least one selected from the group consisting of azomethine-based and azomethineazo-based organic dyes.
透過性色素が、アゾ系、アゾメチンアゾ系およびペリレ
ン系の有機黒色色素からなる群から選ばれた少なくとも
一種である請求項１に記載の近赤外線反射性複合顔料。3. The near-infrared ray according to claim 1, wherein the near-infrared reflective and / or near-infrared transparent dye is at least one selected from the group consisting of azo, azomethineazo and perylene organic black dyes. Reflective composite pigment.
透過性色素が、下記一般式（Ｉ）で表わされる黒色顔料
である請求項１に記載の近赤外線反射性複合顔料。 （但し、式中のＲは炭素数１〜３の低級アルキル基およ
び炭素数１〜３の低級アルコキシル基からなる群から選
ばれた基を表わし、ｎは１〜５の整数を表し、ｎが２以
上のときはＲは同じでも異なっていてもよい。）4. The near-infrared reflective composite pigment according to claim 1, wherein the near-infrared reflective and / or near-infrared transparent dye is a black pigment represented by the following general formula (I). (Wherein, R in the formula represents a group selected from the group consisting of a lower alkyl group having 1 to 3 carbon atoms and a lower alkoxyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 5, and n represents When two or more, R may be the same or different.)
を液媒体中に分散させてなる色素分散液と、白色顔料の
粉末または白色顔料分散液とを混合し、乾燥することを
特徴とする近赤外線反射性複合顔料の製造方法。5. A method comprising mixing a pigment dispersion obtained by dispersing the pigment according to claim 2 in a liquid medium, a white pigment powder or a white pigment dispersion, and drying. A method for producing a near-infrared reflective composite pigment, comprising:
分散剤を含有している請求項５に記載の近赤外線反射性
複合顔料の製造方法。6. The method for producing a near-infrared reflective composite pigment according to claim 5, wherein the dye dispersion according to claim 5 contains a polymer dispersant.
ン性基、ノニオン性基、または上記のイオン性基の何れ
かとノニオン性基を有する重合体である請求項６に記載
の近赤外線反射性複合顔料の製造方法。7. The near-infrared reflection according to claim 6, wherein the polymer dispersant is an anionic group, a cationic group, a nonionic group, or a polymer having any one of the above ionic groups and a nonionic group. Production method of functional composite pigment.
に記載の近赤外線反射性複合顔料を含むことを特徴とす
る近赤外線反射性被覆剤。8. A near-infrared reflective coating comprising the near-infrared reflective composite pigment according to any one of claims 1 to 4 as a coloring agent.
の近赤外線反射性被覆剤。9. The near-infrared reflective coating according to claim 8, which is a paint or an ink.
近赤外線反射性被覆剤で被覆されていることを特徴とす
る近赤外線反射材。10. A near-infrared reflective material, wherein the surface of a substrate is coated with the near-infrared reflective coating material according to claim 8 or 9.
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|---|---|---|---|
| JP2001331248A JP4097926B2 (en) | 2000-12-21 | 2001-10-29 | Manufacturing method of near-infrared reflective composite pigment |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005132462A (en) * | 2003-10-31 | 2005-05-26 | Nippon Foil Mfg Co Ltd | Packaging aluminum foil with printed display having superior infrared permeability |
| JP2005132460A (en) * | 2003-10-31 | 2005-05-26 | Nippon Foil Mfg Co Ltd | Packaging aluminum foil with printed display having superior infrared permeability |
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